Pesticidal compositions and methods of killing pests using o-alkyl-s-(beta-alkoxyethyl)-s-(alkoxy or phenoxy-alkyl) phosphoro dithiolates

ABSTRACT

O-ALKYL-S-(B-ALKOXYETHYL)-S-(AKOXY OR PHENOXYALKYL) PHOSPHORO DITHIOLATES OF THE GENERAL FORMULA   R2-O-C2H4-S-P(=O)(-O-R1)-S-A-O-R3   IN WHICH R1 IS METHYL O ETHYL, R2 IS LOWER ALKYL, R3 IS LOWER ALKYL OR   (X)N-PHENYL   WHEREIN N IS 0 TO 3 AND X IS HALOGEN, LOWER ALKYL OR NITRO, AND A IS LOWER ALKYLENE, WHICH POSSESS INSECTICIDAL, ACARICIDAL AND NEMATOCIDAL PROPERTIES.

US. Cl. 424-217 9 Claims ABSTRACT OF THE DISCLOSUREO-alkyl-S-(fi-allroxyethyl)-S-(alkoxy or phcnoxyalkyl) phosphorodithiolates of the general formula RIO-P S-A- R (I) in which R is methylor ethyl, R is lower alkyl,

R is lower alkyl or wherein nis0to3and X is halogen, lower alkyl ornitro, and A is lower alkylene,

which possess insecticidal, acaricidal and nematocidal properties.

This application is a division of application Ser. No. 196,748, filedNov. 8, 1971, now pending.

The present invention relates to and has for its objects the provisionof particular new 'O-alkyl-S-(/i-alkoxyethyl)- S-(alkoxy orphenoXy-alkyDphosphoro dithiolates wherein the phenyl radical, ifpresent, may be substituted by up to three halogen, alkyl or nitrogroups, which possess insecticidal, acaricidal and nematocidalproperties, active compositions in the form of mixtures of suchcompounds with solid and liquid dispersible carrier vehicles, andmethods for producing such compounds and for using such compounds in anew way especially for combating pests, e.g. insects, acarids andnematodes, with other, and further objects becoming apparent from astudy of the within specification and accompanying examples.

:From the specification of Dutch Pat. No. 67/ 17383 it is known that thecompound of the formula 0 r 0,1150% s (321148 0211, has insecticidal andfungicidal activities.

The present invention provides, as new compounds, the phosphoric acidesters of the general formula States Patent 0 in which R is methyl orethyl, R is lower alkyl, R is lower alkyl or nis0to3and X is halogen,lower alkyl or nitro, and A is lower alkylene.

moo ms s M is a metal equivalent or an ammonium group is reacted with ahalide of the general formula wherein (II) in which (III) in which Halis halogen, preferably chlorine or bromine,

or (b), as a preferred alternative in those cases where R is identicalto IR and A is ethylene, a mercaptan of the general formula HSC H OR.(IV) is reacted, in the form of a metal or ammonium salt thereof or inthe presence of an acid-binding agent, with a phosphoric acid esterdichloride of the general formula In the foregoing Formulas II to V, R RR and A have the meanings stated for Formula I.

Preferably, the reactants are used in substantially amounts shown in thebelow-mentioned reaction scheme.

In either of the process variants of this invention, the reaction ispreferably carried out in the presence of a solvent or diluent. .Forthis purpose, all inert solvents or diluents are suitable, especiallywater; aliphatic, alicyclic and aromatic optionally chlorinatedhydrocarbons such as hexane, cyclohexane, petroleum ether, ligroin,benzene, toluene, xylenes, methylene chloride, chloroform, carbontetrachloride, mono-, diand tri-chloroethylenes and chlorobenzene;ethers, such as diethyl ether, methylethyl ether, di-isopropyl ether,dibutyl ether, ethylene oxide, dioxane and tetrahydrofurane; ketones,such as acetone, methylethyl ketone, methylisopropyl ketone, andmethylisobutyl ketone; alcohols such as methanol, isopropanol,

' butanol and ethylene glycol; nitriles such as acetonitrile,

propionitrile and acrylonitrile; esters such as ethyl acetate and amylacetate; acid amides such as dimethyl formamide and dimethyl acetamide;and sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane.

In either of the above process variants the reaction may be eifected attemperatures within a fairly broad range: generally, the reaction iscarried out at from above 20 C. to the boiling point of the reactionmixture, preferably at from about to 100 C. or to the boiling point ofthe reaction mixture, whichever is the lower.

Both process variant (a) and process variant (b) are preferably carriedout under atmospheric pressure, although it is possible to conducteither reaction under elevated or reduced pressure.

The reaction process variant (a) is illustrated by the followingequation:

R\ /0 l: /P{ M Hal-A-OR moozms s (II) (III) \P-S-AOR' M Hal R 0 ozrns(VI) in which R R R A and M have the meanings stated above. M ispreferably ammonium or an alkali metal.

As examples of the dithiophosphates of the Formula II, there may bementioned the potassium, sodium and ammonium salts ofO-methyl-S-(B-ethoxyethyl)-dithiophosphoric acid,O-ethyl-S-(fi-methoxyethyl)-dithiophosphoric acid, O-ethyl-S-(8-thoxyethyl)-dithiophosphoric acid,O-ethyl-S-(B-isopropoxyethyl)dithiophosphoric acid andO-ethyl-S-(B-n-butoxyethyl)-dithiophosphoric acid.

As examples of the halides of the Formula III, there may be mentioned4-chlorophenoxymethyl chloride, 2,4- dichlorophenoxy methyl chloride,fl-methoxyethyl chloride, fi-ethoxyethyl chloride, fl-isopropoxyethylchloride, fl-n-butoxyethyl chloride, p-phenoxyethyl chloride, fl-(Z-chlorophenoxy)ethyl chloride, fi-(4-chlorophenoXy)-ethyl chloride, 5(2,4 dichlorophenoxy)ethyl chloride, ,8- (2,4,5 trichlorophenoxy)ethylchloride, #3 (4-tert.- butylphenoxy)ethyl chloride, 3(3-methyl-4-chlorophenoxy)ethyl chloride, B--(4-nitrophenoxy)ethylchloride; y-phenoxypropyl chloride and the corresponding bromides.

The reaction of process variant '(b) is illustrated by the followingequation:

( (IV-a) 0 Salmon R o-P M'-o1 S CZHIO R2 (Ia) (VII) in which R and Rhave the meanings stated above, and M is hydrogen, ammonium or a metal,preferably an alkali metal.

As examples of the phosphoric acid ester dichlorides of the Formula V,there may be mentioned O-methyl-phosphoric acid dichloride andO-ethylphosphoric acid dichloride. As examples of the mercaptans of theFormula IV, there may be mentioned B-rnethoxyethyl mercaptan, ,8cthoxyethyl mercaptan, p isopropoxyethyl mercaptan 4 i I, andfl-n-butoxyethyl mercaptan; the sodium, potassium and ammonium salts ofthese mercaptans are also suitable.

As stated above, process variant (b) may be carried out in the presenceof an acid-binding agent according to need. As the acid-binding agentthere may be used a hydroxide, carbonate, bicarbonate or alcoholate ofan alkali metal, or a tertiary amine, such as triethylamine,dimethylaniline or pyridine. When the reaction is carried out in theabsence of an acid-binding agent, the intended prodnot can be obtainedby forming in advance a salt, preferably an alkali metal or ammoniumsalt, of the appropriate mercaptan and then reacting the salt with theappropriate O-alkyl phosphoric acid dichloride.

The compounds of this invention, as implied above, exhibit excellentbiological activities against various harmful insects, spider mites andnematodes. Insecticidally, the compounds of this invention appear to besuperior to the known compound of the Formula A given above and to otherknown compounds having similar directions of activity.

Furthermore, the active compounds of this invention exhibit only a verylow toxicity towards warm-blooded animals and show no phytotoxicitytowards cultivated plants. They are characterized by an activity thatsets in quickly and that is long-lasting. Accordingly, they can be usedfor controlling harmful insects, such as biting and sucking insects,mites and nematodes in agriculture.

For instance, the active compounds of this invention are effective forcontrolling insects belonging to the Coleoptera such as the rice weevil(Sitophilus oryzae), flour beetle (Tribolium castaneum),twenty-eight-spotted lady beetle (Epilachna vigintioctopunctata), barleywireworm (Agriotes fusicicollis) and soy bean beetle (Ana malarufocuprea); insects belonging to the Lepidoptera such as the gypsy moth(Lymcmtria dispar), tent caterpillar (Malacosoma neustria testacea),common cabbageworm (Pieris rapae crucivora), cotton worm or tobaccocutworm (Prodenia litura), rice stem borer (Chilo suppressalis), smallertea tortrix (Adoxophye s orana) and almond moth (Ephestia cautella);insects belonging to the Hemiptera such as the green rice leaf-hopper(Nepho Iettix cincticeps), brown planthopper (Nilaparvata lugens),comstock mealybug (Pseudococcus comstocki), arrowhead scale (Unaspisyanonensis), green peach aphid (Myzus persicae), apple aphid (Aphispomi) and cabbage aphid (Brevicoryne brassicae); insects belonging tothe Orthoptera such as the German cockroach (Blattella germanz'ca)American cockroach (Periplaneta americana) and African mole cricket(Gryllotalpa africana); insects belonging to the Isoptera such as theJapanese termite (Leucotermes speratus); insects belonging to theDiptera such as the house fly (Musca domestica vicina), yellowfevermosquito (Aedes aegypti), seed-corn maggot (Hylemya platura), northernhouse mosquito (Culex pipiens), Chinese malaria mosquito (Anophelessinensis) and smaller house mosquito ('Culex tritaeniorchynchus); mitessuch as the two spotted spider mite (Tetranychus relarius), citrus redmite (Panonychus citri) and Japanese citrus rust mite (Aculuspelekassi); and nematodes such as the southern root-knot nematode(Meloidogyne incag active compounds with conventional pesticidedispersible liquid diluent carriers and/0r dispersible solid carriersoptionally with the use of carrier vehicle assistants, e.g. conventionalpesticide surface-active agents, including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents. Thefollowing may be chiefly considered for use as conventional carriervehicles for this purpose: aerosol propellants which are gaseous atnormal temperatures and pressures, such as halogenated hydrocarbons,e.g. Freon; inert dispersible liquid diluent carriers, including inertorganic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene,xylene, dimethylnaphthalene, aromatic naphtha, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes,etc.), aliphatic and alicyclic hydrocarbons, e.g. n-hexane, cyclohexane,gasolines for industrial use such as petroleum ether and solventnaphtha, and petroleum fractions such as paraffin wax, kerosene, lightoil, middle oil and heavy oil, halogenated aliphatic hydrocarbons (e.g.,methylene chloride, ethylene dichloride, carbon tetrachloride,trichloroethylene, ethylene dibromide, etc.), alcohols (e.g., methanol,ethanol, propanol, butanol, ethylene glycol, etc.), amines (e.g.,ethanolamine, etc.), ethers, (e.g., ethyl ether, ethylene oxide,dioxane, etc.) ether-alcohols (e.g., glycol monomethyl ether, etc.),esters (e.g., ethyl acetate, amyl acetate, etc.), amides (e.g., dimethylformamide, dimethyl acetamid'e, etc.), sulfoxides (e.g., dimethylsulfoxide, etc.), ketones (e.g., acetone, isophorone, methyl ethylketone, cyclohexanone, etc.), and/or water; as well as inert dispersiblefinely divided solid carriers, such as vegetable powders, ground naturalminerals (e.g., kaolins, clays, alumina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, kieselguhr, pyrophyllite,mica, gypsum, calcite, vermiculite, dolomite, muscovite, apatite, slakedlime, magnesium hydroxide, sulfur and pumice) and ground syntheticminerals (e.g., highly dispersed silicic acid) silicate, (e.g., alkalisilicates, synthetic alumina, etc.), synthetic resins such as phenol,urea and vinyl chloride resins; whereas the following may be chief 1yconsidered for use as conventional carrier vehicle assistants, e.g.,surface-active agents, for this purpose: emulsifying agents, such asnonionic and/or anionic emulsifying agents (e.g., polyethylene oxide aswell as ether and esters thereof such as polyoxyethylene esters of fattyacids such as sorbitan monolaurate polyethylene oxide ethers of fattyalcohols and alkyl phenols, alkyl sulfates such as sodium laurylsulfate, alkyl sulfonates, aryl sulfonates, alkyl aryl sulfonates suchasmsodium alkyll naphthalene sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.);cationic surfactants such as alkyl amines (e.g., lauryl amine, stearyltrimethyl ammonium chloride and alkyl dimethyl benzyl ammonium chloride)and polyoxyethylene alkyl amines; amphoteric surfactants; and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides,insecticides and nematocides, or fungicides, bactericides, rodenticides,herbicides, fertilizers, growth-regulating agents, or antiviral agentswhich classes of materials include organic phosphorus acid esters,carbamates, dithio-(or thiol-)carbamates, chlorinated organic compounds,dinitro compounds, organosulfur or organometal compounds, antibiotics,substituted diphenyl ethers, ureas and triazines.

, The novel compounds may also be combined with ad juvants such asorganic matter, stabilizers, adhesive agents, for example agriculturalsoap, calciumcaseinate, sodium alginate, polyvinyl alcohol, detergents,coumarone (or indene) resins or polyvinyl butyl ether, combustiblematerials (for fumigants), for example zinc dust or dicyandiamide,oxygen-yielding substances, for example perchlorates, nitrites ordichromates, phytotoxicity-reducing substances, for example zincsulfate, ferrous chloride or copper nitrate, substances for prolongingthe biological effect, for example chlorinated terphenyls,emulsion-stabilizing substances, for example casein, gum tragacanth andcarboxymethyl cellulose (polyvinyl alcohol also being suitable for thispurpose), and synergistic agents.

The novel compounds may be applied in the form of particular dosagepreparations for specific application made therefrom, such as solutions,liquors, emulsions, suspensions, wettable powders, wettable tablets,soluble powders, pastes, dusts,'granules, fumigating agents and smokingagents which are thus ready for application in any usual manner, forinstance by spraying such as liquid spraying, misting, atomizing,dusting, scattering, watering, pouring, fumigating, soil applicationsuch as mixing, sprinkling, vaporizing and irrigating, surfaceapplication such as painting, banding and dressing (dustcoating),dipping and baiting.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-96% by weight, andpreferably 05-90% by Weight, of the mixture, whereas carrier compositionmixtures suitablefor direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.0001-20%, preferably 0.005l0%, by weightof the mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as ('1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e.g. a surfaceactive agent, suchas an emulsifying agent and/or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.000l%, and preferably ODDS-95%, by weightof the mixture. l

The active compounds can also be used in accordance with the well knownultra-low volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50- microns or evenless, i.e. mist form, for example by airplane crop spraying techniques.Only up to at most about a few liters/hectare are needed, and oftenamounts only up to about 30 to 10,000 g./hectare, preferably 300 to 6000g./hectare, are sufiicient. In this process it is possible to use highlyconcentrated liquid compositions with said liquid carrier vehiclescontaining from about 20 to about 95% by weight of the active compoundor eventhe 100% active substance alone, e.g. about 20-100% by weight ofthe active compound. 1

Furhermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects, acarids andnematodes, which comprises applying to at least one of correspondingly(a) sucli insects, (b) such acarids, (e) such nematodes, and (d) thecorresponding habitat thereof, i.e. the locus to be protected, acorrespondingly combative or toxic amount, i.e. an insecticidally,acaricidally or nematocidally eifective amount of the particular activecompound of the invention alone or together with a carrier vehicle asnoted above.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The preparation of the particular new compounds of dithiolate, having arefractive index ti of 1.5690 and TABLE I.

(Ill/S 02114011 ROP\ (I) S-A-O R Compound number R A v R R Physicalconstants CH! C2114 C2115 02H C2115 02H CH3 CH3 CzHa 02H; CH: CaHu 02H;H; CzHa 0311 -180 02H; C211 CaH7-lS0 CaHv-lSO B-P. 145149 C./O.1 mm. Hg71]) 1.4900 CaHu 02H CAHo-ll C Hg-n no" 1.4881

8 02 CHI CaHs Cl 11:)"1-5535 9. CgHs CH2 C 11 Cl ..;:......:.:.:'.:.:r.:229 1.563!) 10. CaHu CaH| CzHi Q :;;;t;.;.....:... "D" 1.5413

11-....: CaH 03H 02H; Cl m) 1.5572

12- CaHs 02H; CaHi Q 1 --r---:---:---r-----:-::.:..--: np"1.5541

13 CgHg 02H CHHSQ SBIIIBQSSDOVQ. v 71.13 1.5520

14.. OH: C2114 02H; 1 my" 1.5770

16.....-: (33H: Cal-I4 CaHr Cl no" 1.5780

17- CaHs CzHa CaHs :r...:.:r.:....:..:.: my" 1 5350 -04H9-t91t 18 CaHaCaH: CzHn H: :.:...I.:.:::.:::.:..::...:.:.:.: m)" 1.5575

19 C H C H4 C2Ha I :...32..;.::.:.....:.:....:;:. my" 1.5695

' EXAMPLE 1 27 g. of potassium O-ethyl-S-(fl-ethoxyethyl)dithiophosphatewere dissolved in 100 ml. of ethanol and 27 g. of 2,4dichlorophenoxyethyl bromide were added to the solution. Then, themixture was agitated at 75 C. for 3 hours to complete the reaction. Theresulting inorganic salt was separated by filtration, and the ethanolwas distilled off from the filtrate under reduced pressure. 150 ml. ofbenzene were added to the residue, and the mixture was washed with waterand 1% potassium carbonate, and dried over anhydrous sodium sulfate.Distillation of benzene gave 37 g. of a colorless oil,O-ethyl-S-(B-ethoxyethyl) S [fi (2,4-dichlorophenoxy)ethyl]phosphorodithiolate, having a refractive index n of 1.5690 and havingthe formula:

" o sozmoom.

CzHgO-P v s came-@421 EXAMPLE 2 After completion of the dropwiseaddition the temperature of the mixture was gradually raised and themixture was agitated at 70 C. for 1 hour to complete the reaction. Thereaction mixture was then cooled to room temperature, washed with water,1% hydrochloric acid and 1% potassium carbonate, and dried overanhydrous sodium sulfate. Distillation of benzene gave 26 g. of O- ethylS,S di (B ethoxyethyl) phosphorodithiolate boiling at 141-144 C. under0.1 mm. Hg, having a refractive index u of 1.5000 and having theformula:

I CgH50-P EXAMPLE 3 The pesticidal compositions ofthis invention areillustrated in and by the following examples, in which the activecompounds are identified by the numbers assigned to them in Examples1-3.

mm. were put into a rotary mixer and a solution of parts of Compound No.6 in an organic solvent was sprayed onto the particles being rotated,thereby wetting the particles homogeneously. The particles were thendried at 40-50 C. to form coated granules. They were applied 5 EXAMPLE 4by Spraying 15 parts of Compound No. 20, 80 parts 1 of a 1:5 mixture ofdiatomaceous earth and kaolin and 5 parts of an EXAMPLE 1o emulsifierRunnox (a polyoxyethylene alkyaryl ether) were ground and mixed togetherto form a wettable pow- 0.5 part of Compound No. 12, 20 parts ofVelsicol der. It was diluted to 0.05% before application. (ahigh-boiling-point aromatic hydrocarbon) and 79.5

parts of Deobase (deodorized kerosene) were mixed EXAMPLE 5 withstirring to form an oil preparation. It was applied by spraying.

30 Paris of g N 2 of i 30 The excellent pesticidal activity of thecompounds of parts of Kawakazol (a high-boiling-polnt a romatlti ythiinvention is illustrated in and by the following test drocarbon), and 10parts of an emulsifier Sorpol examples, in which the active compoundsare identified by Polyoxyethylene alkylafyl ether) mlxed wlth, thenumbers assigned to them in Examples 1-3. ring to form an emulsifiablepreparation. It was diluted to 0.05% with water before application.EXAMPLE 11 EXAMPLE 6 2 parts of Compound 5 and 98 parts of a 13 Test oneifects against tobacco cutworm larvae ture of talc and clay were groundand mixed together to form a dust. This was applied by scattering viadusting Preparation of sample formulation: equipment.

EXAMPLE 7 Solvent: 3 parts by weight of dimethyl formamide 1.5 parts ofCompound No. 19, 2 parts of an organic z part by welght of alkylarylpolyglycol phosphoric acid ester 0.5 part of isopropyl hydrogenphosphate and 96 parts of a 1:3 mixture of talc and clay were ground andmixed together to form a dust. This was In order to prepare a suitableformulation of an active applied by scattering via dusting equipmentcompound, one part by welght of the active compound was rmxed with theabove amount of the solvent contain- EXAMPLE 8 ing the above amount ofthe emulsifier, and the mixture 25 parts of water were dd to a mixtureof 10 pal-ts was diluted with water to form an aqueous formulation ofCompound No. 8, 10 parts of bentonite, 78 parts of a the active compounda Prescribed 60110611- 1:3 mixture of talc and clay and 2 parts oflignin sultratlol'lfonate. The resulting mixture was intimately blendedand T procedure.Sweet-potato leaves were dipped in a finely di ided b mn of an extruding ra l o t formulation of an emulsifiable liquorcontaining the active obtain granules of 20-40 mesh, followed by dryingat 40- compound at the prescribed concentration, and they were C. Theresulting granules were applied by spraying. then dried in air andplaced in a 9 cm. diameter Petri EXAMPLE 9 dish. Then 10 third-instartobacco cutworm (Proaenia 45 litura) larvae were put into the dish andthe dish was kept 95 parts of clay particles of a size distributlon of0.22 in a thermostat chamber maintained at After 24 1 3 g, term used inthe Examples (4) to (10) means hours had passed, the number of deadlarvae was counted W 0 (a methyb 4 methy1mermp tophenyl and the killingratio was calculated. The results are shown phosphorothioate. in Table2.

TABLE 2 Killing ratio-Active ingredient concen tration 0!- 300 p.p.m.100 p.p.m.

Compound number:

1 100 100 2 100 100 3 100 100 4 10m 100 5 100 100 s 100 100 7 100 100 s100 so 9 100 4o in 100 100 11 100 70 12 100 n 100 60 14 100 20 15 100:.-..;.....--.".'..:1-: 1a 100 10 17 100 a0 is 100 50 in 100 20 so TABLE2-+-Contlnued Killing ratioActive ingredient concen tration 300 p.p.m.100 p.p.m.

Compound (A) 0 (B) 10 0 (C)-- 0 o (D) 0 o (E)- 10 o 1o 0 0 0 v (H) 0 010 0 Slimithion 80 10 Nome:

Compound 7 (B) C|H O\(|? /P---SCH:CHz-O CIH50 CH: 8

(C) 031150 0 ll /PS-CH:CH:O C:H.OCH,CH,OH:S

(D) CQH5O\(IZ') /P'S-CHaCHr-O Q-o C HICHI s v (E) CIHBO O II /PSCHa-O ClCiHsO CHI S (F) clmo o v H /1 8-0 Hr-O Cl CIHEOCHICHICHIS (G)......::CaIhO O ll /P--S-CH2 O-- Ci Q-o 011,011, s

(H) CaHsO O ll P-S-CH:O-C:HI

031150 CH: I '(I) 0550 P-s-omomorn-o-mm cmbocmcrnoms 1'Sumithion=0,0-dimethyl-O-(3-methyl-4-nitropheny1)-phosphorothioate,commercially available comparison.

EXAMPLE 12 EXAMPLE 13 Test on efiects against house-flies Testprocedure.-A sheet of filter paper was spread in a Petri dish of 9 cm.diameter and 1 ml. of an aqueous formulation containing the activecompound at the prescribed concentration and prepared in the same manneras idExainple 11 was, poured into the dish. Then female house-flyimagines were put into the dish and the 'dish was kept for 24 hours in athermostat chamber maintained at 28 C. The number of the dead flies wasthen counted and the killing ratio was calculated. The results are shownin Table 3.

TABLE 3 Killing Ratio (percent)-Active ingredient concentration of-1,000 p.p.m. 100 ppm.

Compound number:

2 100 100 00 100 95 100 100 60 100 70 20 100 60 Compound (A) 0 0 Test oneifects against adzuki bean weevils Test procedure-Ten adzuki beanweevils were soaked for 1 minute in an aqueous formulation containing anactive compound at a prescribed concentration and which had beenprepared in the same manner as in Example 11,

and they were then kept in a thermostat chamber maintained at 28 C. Thenumber of dead weevils was counted after 2 4 hours had passed and thekilling ratio was cal- EXAMPLE 14 Test on effects against carmine mitesIndex 3--No living imago. 2Less than 5% of living imagines compared toan untreated control. 1-5-50% of living imagines compared to theuntreated control. More than 50% of living imagines compared to theuntreated control.

The results are shown in Table 5.

TABLE Control effect index 1,000 p.p.m.

300 p.p.m.

Compound number:

19 Sappilan (CPCBS) Compound (A) 'Sappilan=0hlorophenyl available.

EXAMPLE 15 Test on effects against root-knot nematodes Qeueuuwo:

ONNCDNNJ chlorobenzenesultonate, commercially Preparation of sampleformulation.--2 parts by weight of an active compound were mixed with 98parts by weight of talc, and the mixture was ground to form a dust.

Test procedure-The formulation as prepared above 'was mixed with soiltainted with sweet-potato root-knot nematodes in an amount such that aprescribed concentration of the active compound was obtained in thesoil. The treated soil was stirred and mixed until uniform, and then itwas packed into pots each having an area of acre. Thereafter, about 20tomato seeds (Kurihara variety) were sown per pot and cultivated for 4weeks in a greenhouse. Then each root was drawn out from the soilwithout damaging it. The damage degree caused by the nematodes wasevaluated with respect to roots as one group based on the followingscale.

Damage degree The results are shown in Table 6.

TABLE 6.--EFFECTB AGAINST ROOT-KNOT NEMATODES Knot index: X 100 Knotindex (percent) 30 p.p.m. p.p.m.

Compound number:

4 0 1. 7 '6 0 3. 5 Terracur-p 0. 8 15. 2

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. A method of combating insects, acarids or nematodes which comprisesapplying to the insects, acarids or nematodes or a habitat thereof aninsecticidally, acaricidally or nematocidally effective amount of aphosphoric acid ester of the formula RO-P s-A-O-m (I) in which R ismethyl or ethyl, R is lower alkyl of 1 to 4 carbon atoms, R is loweralkyl of 1 to 4 carbon atoms or wherein n is 0 to 3 and X is chlorine,lower alkyl of l to 4 carbon atoms or nitro, and

A is lower alkylene of 1 to 4 carbon atoms.

2. The method according to claim 1, in which R is methyl or ethyl, R isC -C alkyl, R is C C alkyl, phenyl or phenyl substituted chlorine, C --Calkyl or nitro, and A is methylene, ethylene, propylene, trimethylene ortetramethylene.

3. The method according to claim 1, wherein such compound is O-ethyl-S-fl-methoxyethyl) -S- (fl-ethoxyethyl) phosphorodithiolate of the formulaS C 2H40 C 2H;

4. The method according to claim 1 wherein such compound isO-ethyl-S,S-di-(fi-ethoxyethyl) phosphorodithiolate of the formula 0SC2H4O CQHA! 5. The method according to claim 1 wherein such compound isO-ethyl-:S-(fl-isopropoxyethyl)-S-(fl-ethoxyethyl) phosphorodithiolateof the formula o soimoczm S02E40 CsH1-is0 6. The method according toclaim 1 wherein such compound is O-ethyl-S,S-di-(B-isopropoxyethyl)phosphorodithiolate of the formula 0 30:11) CsH7-ISO S 021140 CSHFiSO 7.The method according to claim 1 wherein such compound is0=ethyl-S-(p-phenoxyethyl)-S-(p-ethoxyethyl) phosphorodithiolate of theformula 8. An insecticidal, acaricidal or nematocidal compositioncomprising an insecticidally, acaricidally or nematocidally effectiveamount of a phosphoric acid ester of the formula R is lower alkyl of lto 4 carbon atoms or wherein n is 0 to 3 and X is chlorine, lower alkylof 1 to 4 carbon atoms or nitro, and

A is lower alkylene of 1 to 4 carbon atoms, in admixture with a diluent.

9. The composition according to claim 8 in which said compound is:

O-ethyl-S-(p'methoxyethyD-S-(fi-ethoxyethyl) phosphorodithiolate,O-ethyl-S,S-di-(p-ethoxyethyl) phosphorodithiolate, O-ethyl-S-p-isopropoxyethyl) -S- fl-ethoxyethyl) phosphorodithiolate,O-ethyl-S,S-di-(fl-isopropoxyethyl) phosphorodithiolate, O-ethyl-S-S-phenoxyethyl) -'S- p-ethoxyethyl) phosphorodithiolate,

O-ethylS-[,8-(4-chlorophenoxy)ethy1]-S-(p-ethoxyethyl)phosphorodithiolate, orO-ethyl-S-[fi-(4-nitr0phenoxy)ethyH-S-(B-ethOXyethyl)phosphorodithiolate.

ALBERT T. MEYERS, Primary Examiner A. J. ROBINSON, Assistant ExaminerPatent No 7 ,9 3 Dated May 1 1974 Inventor) SHIGEO KISHINO ET AL.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Col. 6, line 75, cancel "dithiolate. .and" and substitute the presentinvention and their unexpected superiority and Cols. 7 & 8, Table 1,under heading "A", Compound 2,

II II change 1-1 to H Col. 14, line 29, Claim 2 after "substituted"insert by Signed and sealed this 18th day of March 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTIZ C. MASON Commissioner of Patents attestingOfficer and Trademarks

